WO2019239265A1 - Verre antimicrobien pouvant être traité thermiquement - Google Patents

Verre antimicrobien pouvant être traité thermiquement Download PDF

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Publication number
WO2019239265A1
WO2019239265A1 PCT/IB2019/054734 IB2019054734W WO2019239265A1 WO 2019239265 A1 WO2019239265 A1 WO 2019239265A1 IB 2019054734 W IB2019054734 W IB 2019054734W WO 2019239265 A1 WO2019239265 A1 WO 2019239265A1
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WIPO (PCT)
Prior art keywords
coating
glass substrate
less
glass
resin
Prior art date
Application number
PCT/IB2019/054734
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English (en)
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WO2019239265A9 (fr
Inventor
Liang Liang
Original Assignee
Guardian Glass, LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Guardian Glass, LLC filed Critical Guardian Glass, LLC
Priority to KR1020207032668A priority Critical patent/KR20210019410A/ko
Priority to JP2020563642A priority patent/JP2021526116A/ja
Priority to US16/973,151 priority patent/US20210246069A1/en
Priority to BR112020024941-6A priority patent/BR112020024941A2/pt
Priority to CA3098016A priority patent/CA3098016A1/fr
Priority to EP19742911.1A priority patent/EP3802444A1/fr
Publication of WO2019239265A1 publication Critical patent/WO2019239265A1/fr
Publication of WO2019239265A9 publication Critical patent/WO2019239265A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/29—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/445—Organic continuous phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C03C2217/452—Glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/477—Titanium oxide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/478—Silica
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
    • C03C2217/485—Pigments
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/31—Pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment

Definitions

  • Glass articles have many applications, including use in buildings and furniture.
  • such glass is formed by applying a coating formulation containing a binder and glass frit to the surface of a glass substrate and then thermally treating the substrate to remove the carrier or solvent.
  • additional treatments such as acid etching, mechanical polishing, sandblasting, and polymer film covering, have been used in order to form a translucent coating.
  • conventional methods for forming translucent coatings often suffer from shortcomings such as the inability to adjust the roughness of the coating, the inability to further temper the glass, and the need to avoid controlled etching of products.
  • one embodiment of the present disclosure is directed to a coated glass substrate comprising a coating containing at least one metal oxide containing a zinc oxide.
  • the zinc of the zinc oxide is present in an amount of from 5 wt.% to 50 wt.% as determined according to XPS.
  • the coated glass substrate has area surface roughness S a or S q of from about 5 nm to about 1 ,500 nm as determined via atomic force microscopy.
  • FIG. 1 is a view of a Scanning Electron Microscope (SEM) picture of a coating according to the present disclosure
  • FIG. 2 is a graph showing an example of a particle size distribution of glass frit according to the present disclosure
  • FIG. 3 is a graph showing the self-cleaning performance of an example prepared according to the present disclosure
  • FIG. 4 shows two charts displaying antimicrobial performance of examples according to the present disclosure
  • FIG. 5 is a flow diagram showing the method of forming a coated substrate according to the present disclosure.
  • FIG. 6 is an X-Ray photoelectron spectroscopy spectrum of an example of a coating according to the present disclosure.
  • Alkyl refers to a monovalent saturated aliphatic hydrocarbyl group, such as those having from 1 to 25 carbon atoms and, in some embodiments, from 1 to 12 carbon atoms.
  • Cy-yalkyl refers to alkyl groups having from x to y carbon atoms.
  • This term includes, by way of example, linear and branched hydrocarbyl groups such as methyl (CH3), ethyl (CH3CH2), n-propyl (CH3CH2CH2), isopropyl ((CH3)2CH), n-butyl (CH3CH2CH2CH2), isobutyl ((CH3)2CHCH2), sec-butyl ((CH3)(CH3CH2)CH), t-butyl ((CH3)3C), n-pentyl (CH3CH2CH2CH2CH2), neopentyl ((CH3)3CCH2), hexyl (CH3(CH2CH2CH2)5), etc.
  • linear and branched hydrocarbyl groups such as methyl (CH3), ethyl (CH3CH2), n-propyl (CH3CH2CH2), isopropyl ((CH3)2CH), n-butyl (CH3CH2CH2CH2), isobuty
  • (Cx-Cy)alkenyl refers to alkenyl groups having from x to y carbon atoms and is meant to include for example, ethenyl, propenyl, 1 ,3-butadienyl, and so forth.
  • Aryl refers to an aromatic group, which may have from 3 to 14 carbon atoms and no ring heteroatoms and having a single ring (e.g., phenyl) or multiple condensed (fused) rings (e.g., naphthyl or anthryl).
  • a single ring e.g., phenyl
  • multiple condensed (fused) rings e.g., naphthyl or anthryl.
  • the term“Aryl” applies when the point of attachment is at an aromatic carbon atom (e.g., 5, 6, 7, 8
  • tetrahydronaphthalene-2-yl is an aryl group as its point of attachment is at the 2- position of the aromatic phenyl ring).
  • Cycloalkyl refers to a saturated or partially saturated cyclic group, which may have from 3 to 14 carbon atoms and no ring heteroatoms and having a single ring or multiple rings including fused, bridged, and spiro ring systems.
  • the term“cycloalkyl” applies when the point of attachment is at a non-aromatic carbon atom (e.g., 5,6,7,8,-tetrahydronaphthalene-5-yl).
  • cycloalkyl includes cycloalkenyl groups, such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, and cyclohexenyl.
  • Halo or“halogen” refers to fluoro, chloro, bromo, and iodo.
  • Haloalkyl refers to substitution of an alkyl group with 1 to 5, or in some embodiments, from 1 to 3 halo groups.
  • Heteroaryl refers to an aromatic group, which may have from 1 to 14 carbon atoms and 1 to 6 heteroatoms selected from oxygen, nitrogen, and sulfur and includes single ring (e.g., imidazolyl) and multiple ring systems (e.g., benzimidazol-2-yl and benzimidazol-6-yl).
  • heteroaryl For multiple ring systems, including fused, bridged, and spiro ring systems having aromatic and non-aromatic rings, the term“heteroaryl” applies if there is at least one ring heteroatom and the point of attachment is at an atom of an aromatic ring (e.g., 1 ,2,3,4-tetrahydroquinolin-6-yl and 5,6,7,8-tetrahydroquinolin-3-yl).
  • the nitrogen and/or the sulfur ring atom(s) of the heteroaryl group are optionally oxidized to provide for the N oxide (N 0), sulfinyl, or sulfonyl moieties.
  • heteroaryl groups include, but are not limited to, pyridyl, furanyl, thienyl, thiazolyl, isothiazolyl, triazolyl, imidazolyl, imidazolinyl, isoxazolyl, pyrrolyl, pyrazolyl, pyridazinyl, pyrimidinyl, purinyl, phthalazyl, naphthylpryidyl, benzofuranyl,
  • tetrahydroquinolinyl isoquinolyl, quinazolinonyl, benzimidazolyl, benzisoxazolyl, benzothienyl, benzopyridazinyl, pteridinyl, carbazolyl, carbolinyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenoxazinyl, phenothiazinyl, and phthalimidyl.
  • Heterocyclic or“heterocycle” or“heterocycloalkyl” or“heterocyclyl” refers to a saturated or partially saturated cyclic group, which may have from 1 to 14 carbon atoms and from 1 to 6 heteroatoms selected from nitrogen, sulfur, or oxygen and includes single ring and multiple ring systems including fused, bridged, and spiro ring systems.
  • heterocyclic For multiple ring systems having aromatic and/or non aromatic rings, the terms“heterocyclic”,“heterocycle”,“heterocycloalkyl”, or “heterocyclyl” apply when there is at least one ring heteroatom and the point of attachment is at an atom of a non-aromatic ring (e.g., decahydroquinolin-6-yl).
  • the nitrogen and/or sulfur atom(s) of the heterocyclic group are optionally oxidized to provide for the N oxide, sulfinyl, sulfonyl moieties.
  • heterocyclyl groups include, but are not limited to, azetidinyl, tetrahydropyranyl, piperidinyl, N-methylpiperidin-3-yl, piperazinyl, N- methylpyrrolidin-3-yl, 3-pyrrolidinyl, 2-pyrrolidon-1-yl, morpholinyl, thiomorpholinyl, imidazolidinyl, and pyrrolidinyl.
  • an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, or heterocyclyl group may be substituted with from 1 to 8, in some embodiments from 1 to 5, in some embodiments from 1 to 3, and in some embodiments, from 1 to 2 substituents selected from alkyl, alkenyl, alkynyl, alkoxy, acyl, acylamino, acyloxy, amino, quaternary amino, amide, imino, amidino, aminocarbonylamino, amidinocarbonylamino, aminothiocarbonyl,
  • phosphorodiamidate phosphoramidate monoester, cyclic phosphoramidate, cyclic phosphorodiamidate, phosphoramidate diester, sulfate, sulfonate, sulfonyl, substituted sulfonyl, sulfonyloxy, thioacyl, thiocyanate, thiol, alkylthio, etc., as well as combinations of such substituents.
  • the present invention is directed to an article that contains a glass substrate and a coating provided on a surface of the substrate that is capable of being heat treated.
  • the coating includes at least one metal oxide containing zinc oxide that is present relatively near the surface of the coating opposite the surface adjacent the glass substrate.
  • the coating includes a relatively roughened surface that allows for an increased active surface area.
  • the coated glass substrate of the present invention can be heat treatable and provide a resulting glass substrate with antimicrobial properties.
  • the coated substrate of the present invention exhibits improved antimicrobial properties because of the distribution of the zinc of the zinc oxide within the coating.
  • the antimicrobial properties can be improved.
  • at least some of the zinc oxide may be found on or near an outer surface of the coating, wherein the outer surface of the coating is opposite the surface adjacent and contacting the glass substrate.
  • the zinc of the zinc oxide may be present in the coating in an amount of about 5 wt.% or more, such as about 10 wt.% or more, such as about 13 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more to about 50 wt.% or less, such as about 40 wt.%% or less, such as about 30 wt.% or less, such as about 20 wt.% or less as determined according to XPS.
  • the metal oxide may also include titanium dioxide.
  • titanium dioxide can be employed to serve as a self-cleaning additive.
  • such titanium may also be found on or near an outer surface of the coating, wherein the outer surface of the coating is opposite the surface adjacent and contacting the glass substrate.
  • the titanium of the titanium dioxide may be present in the coating in an amount of about 0.5 wt.% or more, such as about 1 wt.% or more, such as about 1.5 wt.% or more, such as about 2 wt.% or more, such as about 2.5 wt.% or more to about 10 wt.% or less, such as about 7.5 wt.% or less, such as about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less as determined according to XPS.
  • the use of such metal oxides may provide a coating having a roughened surface.
  • the roughened surface allows for an increase in surface area and thus an increase in the amount of zinc and/or titanium that is exposed for providing an antimicrobial effect.
  • the coating may have a surface roughness of about 5 nm or more, such as about 10 nm or more, such as about 15 nm or more, such as about 25 nm or more, such as about 50 nm or more, such as about 100 nm or more, such as about 250 nm or more, such as about 500 nm or more, such as about 600 nm or more, such as about 750 nm or more to about 1 ,500 nm or less, such as about 1 ,250 nm or less, such as about 1 ,000 nm or less, such as about 900 nm or less, such as about 750 nm or less, such as about 500 nm or less, such as about 400 nm or less,
  • the aforementioned surface area may be a profile roughness.
  • the roughness may be an area roughness.
  • the aforementioned roughness may be an arithmetic average in one embodiment. Alternatively, it may also refer to a geometric average.
  • the distribution of metal oxide(s) and surface roughness may allow for improved antimicrobial properties.
  • the coating may have antimicrobial properties such that glass coated according to the present disclosure as compared to traditional glass exhibits a decrease in bacteria of at least about 85%, such as at least about 87%, such as at least about 90%, such as at least about 92%, such as at least about 94%, such as at least about 96%, such as at least about 98%, such as at least about 99%, such as at least about 99.9%.
  • the coating may exhibit a Logio reduction in bacteria of at least about 1 , such as at least about 2, such as at least about 3, such as at least about 3.5, such as at least about 4, such as at least about 4.5, such as at least about 5, such as at least about 5.5, such as at least about 6.
  • the Logio reduction may be about 8 or less, such as less than about 7.5, such as less than about 7, such as less than about 6.5, such as less than about 6.
  • Such antimicrobial tests can be performed in accordance with JIS Z2801.
  • a tempered coating and article according to the present disclosure may also exhibit enhanced processability.
  • the tempered article may have a cross- hatch adhesion as determined in accordance with ASTM D3359-09 of 3B or higher, such as 4B or higher, such as 5B.
  • the cross-hatch adhesion provides an assessment of the adhesion of the coating to the substrate by applying and removing pressure-sensitive tape over cutes made in the coating.
  • the coating may have a stud pull strength of about 200 pounds per square inch or greater, such as about 300 pounds per square inch or greater, such as about 400 pounds per square inch or greater, such as about 450 pounds per square inch or greater, such as about 500 pounds per square inch or greater, such as about 600 pounds per square inch or greater, such as about 1 ,000 pounds per square inch or less, such as about 900 pounds per square inch or less, such as about 800 pounds per square inch or less.
  • the glass substrate typically has a thickness of from about 0.1 to about 15 millimeters, in some embodiments from about 0.5 to about 10 millimeters, and in some embodiments, from about 1 to about 8 millimeters.
  • the glass substrate may be formed by any suitable process, such as by a float process, fusion, down-draw, roll-out, etc. Regardless, the substrate is formed from a glass composition having a glass transition temperature that is typically from about 500°C to about 700°C.
  • the composition may contain silica (S1O2), one or more alkaline earth metal oxides (e.g., magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), and strontium oxide (SrO)), and one or more alkali metal oxides (e.g., sodium oxide (Na 2 0), lithium oxide (U2O), and potassium oxide (K2O)).
  • silica S1O2
  • alkaline earth metal oxides e.g., magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), and strontium oxide (SrO)
  • alkali metal oxides e.g., sodium oxide (Na 2 0), lithium oxide (U2O), and potassium oxide (K2O)
  • S1O2 typically constitutes from about 55 mol.% to about 85 mol.%, in some embodiments from about 60 mol.% to about 80 mol.%, and in some embodiments, from about 65 mol.% to about 75 mol.% of the composition.
  • Alkaline earth metal oxides may likewise constitute from about 5 mol.% to about 25 mol.%, in some embodiments from about 10 mol.% to about 20 mol.%, and in some embodiments, from about 12 mol.% to about 18 mol.% of the composition.
  • MgO may constitute from about 0.5 mol.% to about 10 mol.%, in some embodiments from about 1 mol.% to about 8 mol.%, and in some embodiments, from about 3 mol.% to about 6 mol.% of the composition, while CaO may constitute from about 1 mol.% to about 18 mol.%, in some embodiments from about 2 mol.% to about 15 mol.%, and in some embodiments, from about 6 mol.% to about 14 mol.% of the composition.
  • Alkali metal oxides may constitute from about 5 mol.% to about 25 mol.%, in some embodiments from about 10 mol.% to about 20 mol.%, and in some embodiments, from about 12 mol.% to about 18 mol.% of the composition.
  • Na 2 0 may constitute from about 1 mol.% to about 20 mol.%, in some embodiments from about 5 mol.% to about 18 mol.%, and in some embodiments, from about 8 mol.% to about 15 mol.% of the composition.
  • the composition may contain aluminum oxide (AI2O3).
  • AI2O3 is employed in an amount such that the sum of the weight percentage of Si02 and AI203 does not exceed 85 mol.%.
  • AI2O3 may be employed in an amount from about 0.01 mol.% to about 3 mol.%, in some embodiments from about 0.02 mol.% to about 2.5 mol.%, and in some
  • the composition may also contain iron oxide (Fe 2 C>3), such as in an amount from about 0.001 mol.% to about 8 mol.%, in some embodiments from about 0.005 mol.% to about 7 mol.%, and in some embodiments, from about 0.01 mol.% to about 6 mol.% of the composition.
  • Fe 2 C>3 iron oxide
  • compositions may include, for instance, titanium dioxide ( PO2), chromium (III) oxide (Cr 2 C>3), zirconium dioxide (Zr0 2 ), ytrria (Y2O3), cesium dioxide (Ce0 2 ), manganese dioxide (Mn0 2 ), cobalt (II, III) oxide (C03O4), metals (e.g., Ni, Cr, V, Se, Au, Ag, Cd, etc.), and so forth.
  • titanium dioxide PO2
  • Cr 2 C>3 zirconium dioxide
  • Zr0 2 zirconium dioxide
  • Y2O3 ytrria
  • cesium dioxide Ce0 2
  • manganese dioxide Mn0 2
  • cobalt (II, III) oxide C03O4
  • metals e.g., Ni, Cr, V, Se, Au, Ag, Cd, etc.
  • a coating is provided on one or more surfaces of the substrate.
  • the glass substrate may contain first and second opposing surfaces, and the coating may thus be provided on the first surface of the substrate, the second surface of the substrate, or both.
  • the coating is provided on only the first surface.
  • the opposing second surface may be free of a coating or it may contain a different type of coating.
  • the coating of the present invention may be present on both the first and second surfaces of the glass substrate. In such embodiments, the nature of the coating on each surface may be the same or different.
  • the coating may be employed such that it substantially covers (e.g., 95% or more, such as 99% or more) the surface area of a surface of the glass substrate.
  • the coating may also be applied to cover less than 95% of the surface area of a surface of the glass substrate.
  • the coating may be applied on the glass substrate in a decorative manner.
  • the coating may contain any number of different materials.
  • the coating may contain a binder and at least one metal oxide containing zinc oxide.
  • the binder may be one produced via sol gel method or may include an interpenetrating polymer network.
  • the zinc oxide may be obtained from different sources, such as via a reaction using another zinc compound (e.g., zinc acetate) or a glass frit.
  • the coating disclosed herein can be produced using any binder generally known in the art.
  • the binder may include one produced via sol-gel by employing an alkoxide.
  • the binder may include an interpenetrating polymer network of at least two crosslinked polymers.
  • the binder may be formed via sol-gel.
  • the binder may be formed from a metal and/or non-metal alkoxide compound.
  • such alkoxides may be employed to form a polymerized (or condensed) alkoxide coating.
  • the compounds may undergo a hydrolysis reaction and a condensation reaction. Then, the solvent is removed by heating or other means to provide the coating.
  • an alkoxide may have the following general formula
  • x is from 1 to 4;
  • R is an alkyl or cycloalkyl
  • M is a metal or a non-metal cation.
  • R, M, and x may be generally selected accordingly, in certain embodiments, they may be selected according to the following.
  • “x” may be from 1 to 4. However,“x” may be selected based upon the valence of the chosen metal or non-metal cation. As indicated above,“x” may be 1 , 2, 3, or 4. In one embodiment,“x” is 1 while in other embodiments,“x” may be 2. In another embodiment,“x” may be 3 while in another embodiment“x” may be 4.
  • “R” may be an alkyl or cycloalkyl.
  • such alkyl may be Ci or greater, such as a C1-C6. , such as a C1-C3, such as a C2-C3.
  • such cycloalkyl may be C3 or greater, such as a C3-C6. , such as a C4-C6, such as a C 4 - C5.
  • “R” is an alkyl
  • “R” may be selected to be a methyl, ethyl, butyl, propyl, or isopropyl group.
  • “R” may be a propyl group, such as an isopropyl group.
  • “R” may be a cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl group.
  • “M” may be a metal cation or a non-metal cation.
  • “M” may be a metal cation.
  • the metal may be a Group IA, IIA, IIIA, IVA, VA, VIA, IB, MB NIB, IVB, VB, VIB, VIIB, or VIIIB metal.
  • “M” while not necessarily limited to the following, may be aluminum, cobalt, copper, gallium, germanium, hafnium, iron, lanthanum, molybdenum, nickel, niobium, rhenium, scandium, silicon, sodium, tantalum, tin, titanium, tungsten, or zirconium.
  • “M” may be copper, aluminum, zinc, zirconium, silicon or titanium. In one embodiment,“M” may include any combination of the aforementioned.
  • the alkoxide may include a combination of alkoxides including copper, aluminum, zinc, zirconium, silicon and titanium.
  • “M” may include at least silicon.
  • “M” may be a non-metal cation, such as a metalloid as generally known in the art.
  • alkoxides may be selected according to the following exemplary embodiments.
  • exemplary alkoxides may include Cu(OR), Cu(OR) 2 , AI(OR) 3 , Zr(OR) 4 , Si(OR) 4 , Ti(OR) 4 , and Zn(OR) 2 , wherein R is a Ci or greater alkyl group.
  • the metal alkoxide may include, but is not limited to, aluminum butoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, zirconium isopropoxide, zirconium propoxide, zirconium butoxide, zirconium ethoxide, tantalum ethoxide, tantalum butoxide, niobium ethoxide, niobium butoxide, tin t-butoxide, tungsten (VI) ethoxide, germanium, germanium isopropoxide, hexyltrimethoxylsilane, tetraethoxysilane, and so forth, and in a more particular embodiment may be titanium isopropoxide, zirconium n-propoxide, aluminum s-butoxide, copper propoxide, and/or tetraethoxysilane.
  • the alkoxide compound may be an organoalkoxysilane compound.
  • organoalkoxysilane compounds include those having the following general formula:
  • a is from 0 to 3, and in some embodiments, from 0 to 1 ;
  • R 5 is an alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, halo, or haloalkyl;
  • R 6 is an alkyl
  • “a” is 0 such that that the organosilane compound is considered an organosilicate.
  • One example of such a compound is tetraethyl orthosilicate (Si(OC 2 Hs) 4 ).
  • “a” is 1 such that the organosilane compound is considered a trialkoxysilane compound.
  • R5 in the trialkoxysilane compound may be an alkyl, aryl, or haloalkyl (e.g., fluoroalkyl).
  • Such group may have at least 1 carbon atom, such as at least 2 carbon atoms, such as at least 3 carbon atoms and may have 25 carbon atoms or less, such as 20 carbon atoms or less, such as 10 carbon atoms or less, such as 5 carbon atoms or less.
  • trialkoxysilane compounds include, for instance, ethyltrimethoxysilane
  • phenyltrimethoxysilane phenyl-(OCH 3 ) 3
  • phenyltriethoxysilane phenyl- (OCH 2 CH 3 ) 3
  • hexyltrimethoxylsilane CH 3 (CH 2 )sSi(OCH 3 ) 3
  • hexyltriethoxylsilane CH 3 (CH 2 ) 5 Si(OCH 2 CH 3 ) 3
  • heptadecapfluoro-1 ,2,2- tetrahydrodecyltrimethoxysilane CF 3 (CF 2 ) 7 (CH 2 ) 2 Si(OCH 3 ) 3
  • 3- glycidoxypropyltrimethoxysilane CH 2 (0)CH-CH 2 0-(CH 2 ) 3 -Si(0CH 3 ) 3 ), etc., as well as combinations thereof.
  • any of a variety of curing mechanisms may generally be employed to form the silicon-containing resin.
  • the alkoxysilanes can undergo a hydrolysis reaction to convert the OR6 groups into hydroxyl groups. Thereafter, the hydroxyl groups can undergo a condensation reaction to form a siloxane functional group.
  • reactions may occur via an SN2 mechanism in the presence of an acid. For instance, silanes may be hydrolyzed and then
  • the hydrolyzed silanes may also react with silica particles, such as silica nanoparticles, when employed.
  • the organosilane compound may initially be dissolved in a solvent to form a solution.
  • organic solvents such as hydrocarbons (e.g., benzene, toluene, and xylene); ethers (e.g., tetrahydrofuran, 1 ,4-dioxane, and diethyl ether); ketones (e.g., methyl ethyl ketone); halogen-based solvents (e.g., chloroform, methylene chloride, and 1 ,2- dichloroethane); alcohols (e.g., methanol, ethanol, isopropyl alcohol, and isobutyl alcohol); and so forth, as well as combinations of any of the foregoing.
  • hydrocarbons e.g., benzene, toluene, and xylene
  • ethers e.g., tetrahydrofuran, 1 ,4-dioxane, and die
  • Alcohols are particularly suitable for use in the present invention.
  • concentration of the organic solvent within the solution may vary, but is typically employed in an amount of from about 70 wt.% to about 99 wt.%, in some embodiments from about 80 wt.% to about 98 wt.%, and in some embodiments, from about 85 wt.% to about 97 wt.% of the solution.
  • Organosilane compounds may likewise constitute from about 1 wt.% to about 30 wt.%, in some embodiments from about 2 wt.% to about 20 wt.%, and in some embodiments, from about 3 wt.% to about 15 wt.% of the solution.
  • the binder may be produced as an interpenetrating network.
  • the interpenetrating network may include any number of resins.
  • the network may include at least two polymer resins, such as at least three polymer resins, each having a chemical composition different from the other.
  • the interpenetrating network can be a fully-interpenetrating network or a semi-interpenetrating network.
  • the interpenetrating network is a fully-interpenetrating network such that the all of the resins of the network are crosslinked. That is, all of the resins of the binder are crosslinked to form the interpenetrating network.
  • the polymer chains of at least one respective resin are interlocked with the polymer chains of another respective resin such that they may not be separated without breaking any chemical bonds.
  • the interpenetrating network can also be a semi-interpenetrating network.
  • the network contains at one resin whose polymer chains are not interlocked with the polymer chains of a crosslinked resin such that the former polymers chains can theoretically be separated without breaking any chemical bonds.
  • the interpenetrating network may include a combination of an organic crosslinked network and an inorganic crosslinked network.
  • at least one of the crosslinked resins may form an organic crosslinked network while at least one of the crosslinked resins may form an inorganic crosslinked resin.
  • organic crosslinked resin it is meant that the polymerizable compound is a carbon-based compound.
  • inorganic crosslinked resin it is meant that the polymerizable compound is not a carbon-based compound.
  • the polymerizable compound may be a silicon-based compound.
  • the interpenetrating network may include at least two organic crosslinked networks and one inorganic crosslinked network.
  • an interpenetrating network can be synthesized using any method known in the art.
  • a formulation containing all of the polymerizable compounds as well as any other reactants, reagents, and/or additives e.g., initiators, catalysts, etc.
  • the respective crosslinked resins may form at substantially the same time.
  • the aforementioned polymerizable compounds may include individual monomers and oligomers or pre-polymers.
  • An interpenetrating network can also exhibit certain properties that distinguish it from a simple blend of resins.
  • the interpenetrating network may exhibit a glass transition temperature that is between or intermediate the glass transition temperature of any two of the first crosslinked resin, the second crosslinked resin, and the third resin.
  • the interpenetrating network may have a glass transition temperature of from 0°C to 300°C, such as from 10°C to 250°C, such as from 20°C to 200°C, such as from 30°C to 180°C.
  • the glass transition temperature may be measured by differential scanning calorimetry according to ASTM E1356.
  • ASTM E1356 differential scanning calorimetry
  • the resins of the binder may be a thermoplastic resin or a thermoset resin. At least one of the resins in the binder is a thermoset resin such that it can be cured/crosslinked. For instance, by curing, the thermoset resin can become hardened and allow for the formation of a coating.
  • the thermoset resin is generally formed from at least one crosslinkable or polymerizable resin, such as a (meth)acrylic resin, (meth)acrylamide resin, alkyd resin, phenolic resin, amino resin, silicone resin, epoxy resin, polyol resin, etc.
  • the term “(meth)acrylic” generally encompasses both acrylic and methacrylic resins, as well as salts and esters thereof, e.g., acrylate and methacrylate resins.
  • at least two of the resins may be thermoset resins.
  • two of the resins may be thermoset resins while a third resin may be a thermoplastic resin.
  • at least three of the resins may be thermoset resins upon being crosslinked.
  • the interpenetrating network may contain a crosslinked polyol resin.
  • the crosslinked polyol resin can be obtained by reacting or crosslinking polyols.
  • polyols contain two or more hydroxyl groups (i.e., defined as an -OH group wherein the -OH group of a carboxyl group is not considered a hydroxyl group).
  • polyols can be non-polymeric polyols or polymeric polyols.
  • polyols may include, for instance, a diol compound, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyacrylate polyol, a polyurethane polyol, a polysiloxane polyol, a phenolic polyol, a sugar alcohol, a dendritic polyol, and so forth.
  • the polyol may be a diol compound, a polyether polyol, a sugar alcohol, and/or a dendritic polyol.
  • the polyol may not be limited to the aforementioned and may include any polyol known in the art that can be polymerized and/or crosslinked.
  • the polyol may include a diol compound.
  • the polyol may be an ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, etc. While the aforementioned are diol compounds containing two hydroxyl groups, it should be understood that compounds containing additional hydroxyl groups may also be employed.
  • the polyol may include a polyurethane polyol.
  • the polyurethane polyol may be formed by reacting one or more isocyanate groups with a polyol.
  • the polyol may include a polyether polyol.
  • the polyether polyol may include an ethoxylation or a propoxylation product of water or a diol.
  • the polyether polyol may be polyethylene glycol, polypropylene glycol, or a combination thereof. In one embodiment, the polyether polyol may be
  • polyethylene glycol In another embodiment, the polyether polyol may be polypropylene glycol.
  • the propylene glycol may be a monopropylene glycol, dipropylene glycol and/or a tripropylene glycol.
  • the polyol may include a polyester polyol.
  • the polyester polyol may be made by a polycondensation reaction of an acid or corresponding anhydride with a polyhydric alcohol.
  • Suitable acids for example include, but are not limited to, benzoic acid, maleic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid and sebacic acid as well as their corresponding anhydrides, and dimeric fatty acids and trimeric fatty acids and short oils.
  • Suitable polyhydric alcohols include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, 1 ,4-butanediol, 1 ,6-hexane diol, 2, 2-dimethyl-1 , 3-propanediol, neopentyl glycol, tetraethylene glycol, polycarbonate diols, trimethylolethane, trimethylolpropane, glycerol, 1 ,4-cyclohexanediol, 1 ,4-cyclohexanedimethanol, and glycerol.
  • the polyol may include a polyacrylate polyol.
  • the polyacrylate polyol may be made by a copolymerization reaction of a hydroxyalkyl(meth)acrylate monomer, such as, for example, a hydroxy C1-C8 alkyl (meth)acrylate, with an acrylate monomer, such as, for example, a C1-C10 alkyl acrylate and a cyclo C6-C12 alkyl acrylate, or with a methacrylate monomer, such as, for example, a C1-C10 alkyl methacrylate and a cyclo C6-C12 alkyl methacrylate, or with a vinyl monomer, such as, for example, styrene, a- methylstyrene, vinyl acetate, vinyl versatate, or with a mixture of two or more of such monomers.
  • Suitable hydroxyalkyl(meth)acrylate monomers include for example,
  • Suitable alkyl (meth)acrylate monomers include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, butyl acrylate, ethylhexyl methacrylate, isobornyl methacrylate.
  • Suitable polyacrylate polyols include, for example, hydroxy(C2-C8)alkyl
  • the polyol may also include a sugar alcohol.
  • the sugar alcohol may be a sucrose based alcohol.
  • the polyol may be a sorbitol or a sorbitol based polyol.
  • the sorbitol may be an ethoxylated and/or propoxylated sorbitol.
  • the polyol may be a dendritic polyol.
  • the dendritic polyols contain reactive hydroxyl groups with can react with other functional groups.
  • such dendritic polyols can offer a large number of primary hydroxyl groups along a densely branched polymer backbone.
  • the dendritic polyol may be a carbon based dendritic polyol or a silicon based dendritic polyol or a combination thereof. That is, the base polyol utilized for the formation of the dendritic polyol may include carbon, silicon, or a combination thereof. In one embodiment, the base polyol includes carbon.
  • the base polyol includes a combination of a silicon and carbon (i.e., a carbosilane).
  • the base polyol may also include other atoms, such as another oxygen atom outside of the hydroxyl group.
  • the base polyol should be a branched structure. For instance, from a central atom, there should be at least three, such as at least four substituent groups or branches that extend therefrom and allow the formation of a dendritic structure.
  • the dendritic polyol may have an average degree of branching of more than zero and less than or equal to 1., such as from 0.2 to 0.8.
  • strictly linear polyols have a degree of branching of zero and ideally dendritic polyols have a degree of branching of 1.0.
  • the average degree of branching may be determined by 13 C-NMR spectroscopy.
  • the dendritic polyol may be a polyether polyol and/or a polyester polyol.
  • the dendritic polyol may be a polyether polyol.
  • the dendritic polyol may be a polyester polyol.
  • the dendritic polyol may be a combination of a polyether poly and a polyester polyol.
  • the dendritic polyol has at least 2, such as at least 3, such as at least 4, such as at least 5, such as at least 6, such as at least 8, such as at least 10, such as at least 15, such as at least 20, such as at least 30, such as at least 50, such as at least 100 terminal hydroxyl groups to 1000 or less, such as 500 or less, such as 100 or less, such as 75 or less, such as 50 or less, such as 25 or less, such as 15 or less, such as 10 or less terminal hydroxyl groups.
  • the dendritic polyol has a molecular weight of at least 500 g/mol, such as at least 1 ,000 g/mol, such as at least 1 ,500 g/mol, such as at least 2,000 g/mol, such as at least 2,500 g/mol, such as at least 3,000 g/mol, such as at least 4,000 g/mol, such as at least 5,000 g/mol, such as at least 6,000 g/mol, such as at least 10,000 g/mol to 100,000 g/mol or less, such as 75,000 g/mol or less, such as 50,000 g/mol or less, such as 25,000 g/mol or less, such as 15,000 g/mol or less, such as 10,000 g/mol or less, such as 7,500 g/mol or less, such as 6,000 g/mol or less, such as 5,000 g/mol or less. While not necessarily limited, the dendritic polyol may be any of those available under the name BoltornTM.
  • crosslinked networks can be obtained.
  • crosslinked networks can be obtained via a
  • condensation reaction with any silanes, in particular hydrolyzed silanes present in the formulation.
  • reactions may occur with a melamine resin.
  • the dendritic polyol may serve as a crosslinking agent.
  • a carbocation intermediate may be formed in the melamine resin.
  • condensation may occur between the melamine resin and the dendritic polyol.
  • the dendritic polyol may also react with the glass substrate. That is, the dendritic polyol may react with hydroxyl groups present on the glass substrate. Such reaction may improve the adhesive strength of the coating on the glass substrate thereby resulting in improved stud pull and cross-hatch properties.
  • any of a variety of curing mechanisms may generally be employed to form the crosslinked polyol resin.
  • a crosslinking agent may be employed to help facilitate the formation of crosslink bonds.
  • an isocyanate crosslinking agent may be employed that can react with amine or hydroxyl groups on the polyol polymerizable compound.
  • the isocyanate crosslinking agent can be a polyisocyanate crosslinking agent.
  • the isocyante crosslinking agent can be aliphatic (e.g., hexamethylene diisocyanate, isophorone diisocyanate, etc.) and/or aromatic (e.g., 2,4 tolylene diisocyanate, 2,6-tolylene diisocyanate, etc.).
  • the reaction can provide urea bonds when reacting with an amine group and urethane bonds when reacting with a hydroxyl group.
  • the crosslinked polymer or resin may be a polyurethane.
  • a melamine crosslinking agent may be employed that can react with hydroxyl groups on the polyol polymerizable compound to form the crosslink bonds.
  • Suitable melamine crosslinking agents may include, for instance, resins obtained by addition-condensation of an amine compound (e.g., melamine, guanamine, or urea) with formaldehyde.
  • Particularly suitable crosslinking agents are fully or partially methylolated melamine resins, such as hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, etc., as well as mixtures thereof.
  • Such reactions can provide ether bonds when reacting a hydroxyl group of the polyol polymerizable compound with a hydroxyl group of the amine (e.g., melamine) crosslinking agent.
  • the crosslinked polymer or resin may be a polyurethane.
  • the first crosslinked resin is a crosslinked polyol resin with urethane bonds formed by the polyol and the crosslinking agent.
  • the polyol is crosslinked with an isocyanate crosslinking agent.
  • the first crosslinked resin is a crosslinked polyol resin with ether bonds formed by the polyol and the crosslinking agent.
  • the polyol is crosslinked with an amine crosslinking agent containing hydroxyl groups, such as a melamine-formaldehyde crosslinking agent.
  • reactions may occur via an SN1 mechanism in the presence of an acid catalyst (e.g., p-toluene sulfonic acid).
  • an acid catalyst e.g., p-toluene sulfonic acid.
  • a proton can be attacked by an oxygen atom (in -CH 2 OCH 3 ) located in the melamine formaldehyde to generate a carbocation intermediate with -CH 3 OH remaining as the by-product.
  • the nucleophilic oxygen in the polyol can attack the electrophilic carbocation intermediate to create a chemical bond between the melamine-formaldehyde and the polyol.
  • the binder may also contain an acrylate resin.
  • the acrylate resin may be one derived from acrylic acid, methacrylic acid, or a combination thereof.
  • the acrylate monomer includes, but is not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n- butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i- amyl acrylate, isobomyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2- ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohex
  • the acrylate monomers may be diacrylate monomers.
  • the acrylate monomers may be diacrylate monomers including, but not limited to, methyl diacrylate, ethyl diacrylate, n-propyl diacrylate, i-propyl diacrylate, n-butyl diacrylate, s-butyl diacrylate, i-butyl diacrylate, t-butyl diacrylate, n-amyl diacrylate, i-amyl diacrylate, isobomyl diacrylate, n-hexyl diacrylate, 2-ethylbutyl diacrylate, 2-ethylhexyl diacrylate, n-octyl diacrylate, n- decyl diacrylate, methylcyclohexyl diacrylate, cyclopentyl diacrylate, cyclohexyl diacrylate, methyl di methacrylate, ethyl
  • dimethacrylate 2-ethylbutyl dimethacrylate, methylcyclohexyl dimethacrylate, cinnamyl dimethacrylate, crotyl dimethacrylate, cyclohexyl dimethacrylate, cyclopentyl dimethacrylate, 2-ethoxyethyl dimethacrylate, isobornyl dimethacrylate, etc., as well as combinations thereof.
  • the acrylate monomers may be aliphatic monomers.
  • the monomers may be used to form aliphatic oligomers.
  • the aliphatic monomers or oligomers may not contain any aromatic components.
  • the monomers may also include any derivatives of the
  • these monomers can be referred to as the
  • the monomers may be polymerized, including by graft, block, or random
  • a (meth)acrylate copolymer can mean either a methacrylate copolymer or an acrylate copolymer, either in their modified or unmodified form.
  • such a copolymer may comprise any of the acrylate monomers contained herein copolymerized with polyesters, polyvinyl acetates, polyurethanes, polystyrene, or combinations thereof.
  • the co-polymer may include a polystyrene copolymer and more particularly, a meth-methylacrylate and polystyrene copolymer.
  • the acrylate resin is made from monomers including the monoacrylates and the diacrylates. In another embodiment, the monomers consist of the diacrylate monomers.
  • the acrylate resins may also further include a glycidyl functional group.
  • the acrylate monomer may be a glycidyl group containing acrylate monomer such that the glycidyl group is not part of the backbone but instead imparts functionality to the acrylate monomer.
  • these acrylate resins can be synthesized according to any method known in the art.
  • the acrylate resins can be formed in one reaction step or in more than one reaction step. If multiple steps are employed, a prepolymer may be formed initially which can then undergo further reactions to synthesize the acrylate resins disclosed herein. Also, the acrylate resins can be synthesized using UV radiation.
  • the glycidyl or epoxy groups of the resins may be crosslinked. Crosslinking may be performed using any method and using any crosslinking agent generally employed in the art.
  • the crosslinking agent may be an amine, an amide, an acrylate, or a combination thereof. In one embodiment, the crosslinking agent may be an amine.
  • the crosslinking agent may be a diamine, a triamine, or a combination thereof.
  • the crosslinking agent may be an amide.
  • the crosslinking agent may be an acrylate.
  • the acrylate may be an ethoxylated acrylate, such as an ethoxylated trimethylolpropane triacrylate.
  • crosslinking can be employed to improve the integrity of the coating.
  • an initiator e.g., benzoyl peroxide
  • a free radical which can attack a double bond on a crosslinking agent, monomer or oligomer to form free radicals which can then subsequently attack other monomers or oligomers and form a three dimensional crosslinked network.
  • the binder may also contain an epoxy resin.
  • an epoxy resin can be formed using any method generally known in the art.
  • the epoxy resins can be synthesized from any compounds that contain an epoxy component.
  • Such compounds may include at least one epoxide functional group, such as at least two epoxide functional groups.
  • an epoxy compound is a compound that includes epoxide groups and may be reacted or cross-linked. These compounds containing the epoxide functional groups can be referred to as the polymerizable compounds of the epoxy resins.
  • Suitable epoxy resins include, but are not limited to, epoxy resins based on bisphenols and polyphenols, such as, bisphenol A, tetramethylbisphenol A, bisphenol F, bisphenol S, tetrakisphenylolethane, resorcinol, 4,4'-biphenyl, dihydroxynaphthylene, and epoxy resins derived from novolacs, such as, phenokformaldehyde novolac, cresolTormaldehyde novolac, bisphenol A novolac, biphenyl-, toluene-, xylene, or mesitylene-modified phenolTormaldehyde novolac, aminotriazine novolac resins and heterocyclic epoxy resins derived from p-amino phenol and cyanuric acid.
  • epoxy resins derived on bisphenols and polyphenols such as, bisphenol A, tetramethylbisphenol A, bisphenol F, bisphenol S,
  • the epoxy resins may include a diglycidyl ether.
  • the epoxy resins may be non-aromatic hydrogenated cyclohexane dimethanol and diglycidyl ethers of hydrogenated Bisphenol A-type epoxide resin (e.g., hydrogenated bisphenol A-epichlorohydrin epoxy resin), cyclohexane dimethanol.
  • Other suitable non-aromatic epoxy resin may include cycloaliphatic epoxy resins.
  • the epoxy compound may be a combination of an epoxy compound and an acrylate compound.
  • such compound may be an epoxy acrylate oligomer, such as an epoxy diacrylate, an epoxy tetraacrylate, or a combination thereof.
  • such compound may be a bisphenol A epoxy diacrylate, bisphenol A epoxy tetraacrylate, or a combination thereof.
  • acrylate may be any of those referenced herein.
  • the compound may be a bisphenol A epoxy dimethacrylate or a bisphenol A epoxy tetramethacrylate.
  • Such oligomers may also be modified to include a substituent group.
  • such substituent group may include an amine, a carboxyl group (e.g., a fatty acid), etc.
  • the epoxy groups of the resins may be crosslinked using any method and using any crosslinking agent generally employed in the art.
  • the crosslinking agent may be an amine, an amide, an acid, a phenol, an alcohol, etc.
  • the crosslinking agent may be an amine.
  • the crosslinking agent may be a diamine, a triamine, or a combination thereof.
  • the crosslinking agent may be an amide.
  • the crosslinking agent may be an acrylate, such as a diacrylate or a triacrylate.
  • an initiator e.g., benzoyl peroxide
  • the binder may also contain a silicon-containing resin.
  • the silicon-containing resin may be a polysiloxane resin.
  • the polysiloxane resin may be a polysilsesquioxane resin.
  • such a silicon- containing resin can be formed using any method generally known in the art.
  • the silicon-containing resin can be formed by reacting organosilicon compounds, such as organosilane compounds. That is, the organosilicon compounds, such as the organosilane compounds, can be referred to as the polymerizable compounds of the silicon-containing resin.
  • organosilicon compounds may include organosilane compounds, such as alkylsilanes including substituted alkyl silanes.
  • organosilicon compounds may also include organoalkoxysilanes,
  • organosilicon compounds may include a combination of alkylsilane compounds and organoalkoxysilane compounds.
  • organoalkoxysilane compounds include those as the aforementioned organoalkoxysilane compound employed in the binder using the sol-gel process.
  • the silicon-containing resin is made from organosilicon compounds consisting of the organoalkoxysilane compounds as mentioned above.
  • the crosslinked resins form crosslinks with itself. That is, for example, the first crosslinked resin is formed by reacting a polyol with a crosslinking agent.
  • the second crosslinked resin is formed by reacting silicone- containing compounds.
  • one resin may form covalent bonds with another resin.
  • the first crosslinked polyol resin may also have some covalent bonds with another resin, such as the silicon- containing resin.
  • silica particles such as silica nanoparticles, when employed, can also be used to react with the polyol resin to introduce
  • the coating may include at least one metal oxide, which may be included in the coating as a particle or a nanoparticle.
  • the metal oxide may be a metalloid containing particle or nanoparticle, a metal containing particle nanoparticle, or a combination thereof.
  • These particles include, but are not limited to, Si0 2 , Ti0 2 , Zr0 2 , AI 2 C>3, ZnO, CdO, SrO, PbO, Bi 2 C>3, CuO, Ag 2 0, Ce0 2 , AuO, Sn0 2 , etc.
  • any metal oxide particles included in the coating may be in the form of nanoparticles.
  • the metal oxide contains at least zinc oxide. Without intending to be limited by theory, the present inventors have discovered that the zinc can provide the coating with beneficial antimicrobial properties.
  • the antimicrobial properties of zinc oxide may be attributed to having zinc at or near the surface of the coating. Wthout intending to be bound by the theory, zinc and reactive oxygen species may be released to react via an electrostatic interaction with microorganisms at the coating surface.
  • the source of the zinc oxide is not limited by the present invention.
  • the source of the zinc oxide may be a glass frit as defined herein.
  • the zinc oxide may be added to the coating.
  • the zinc oxide may be synthesized via another zinc compound (e.g., zinc acetate) wherein such zinc compound is converted in situ to zinc oxide.
  • the metal oxide may also include titanium dioxide.
  • titanium dioxide may also be present as a nanoparticle.
  • the titanium dioxide can be employed to serve as a self cleaning additive. That is, the titanium dioxide can be employed for cleaning and/or disinfecting surfaces exposed to light.
  • the photocatalytic activity of the titania at a free surface or near-surface region of the coating attributes to the self-cleaning action. Titania is photocatalytically active with ultraviolet radiation and can be used to decompose organic materials from the surface of a coating.
  • the metal oxides may also include aluminum oxide and/or zirconium dioxide. Such oxides may also be present in the form of nanoparticles. Wthout intending to be limited by theory, the aluminum oxide and zirconium dioxide may assist in improving the durability of the glass.
  • the metal oxide contains a silica nanoparticle.
  • the present inventors have discovered that the mechanical strength of the polymer network can be further enhanced by employing such silica nanoparticles and that silica nanoparticle may improve optical qualities of the coating.
  • the silica particle may contain hydroxyl groups that can be condensed with the hydroxyl groups of a silane hydroxyl group of a silanol (e.g., from a hydrolyzed organoalkoxysilane used to form the silicon-containing resin).
  • the silica particles may also react with a carbocation in the polyol resins via a condensation reaction.
  • the silicon-containing nanoparticles may be discrete particles within the coating or may be bonded to a resin.
  • the particles or nanoparticles may be provided in various forms, shapes, and sizes.
  • the average size of the particles and nanoparticles, such as the titanium dioxide or zinc oxide nanoparticles may generally be about 100 microns or less, such as about 50 microns or less, such as about 10 microns or less, such as about 1 micron or less, such as about 500 nanometers or less, such as about 400 nanometers or less, such as about 300 nanometers or less, such as about 200 nanometers or less, such as about 100 nanometers or less to about 1 nanometer or more, such as about 2 nanometers or more, such as about 5 nanometers or more.
  • the average size of a nanoparticle refers to its average length, width, height, and/or diameter.
  • the particles and/or nanoparticles may have a specific surface area is greater than 150 m 2 /g, in some embodiments greater than 200 m 2 /g.
  • the coating may also include a glass frit.
  • the glass frit may help adhere the polymers to the glass substrate.
  • the glass frit may have a melting temperature of from about 400°C to about 700°C, and in some embodiments, from about 500°C to about 600°C.
  • glass frit according to the present disclosure may have a fairly low melting point. The present inventors have unexpectedly found that by using a glass frit with a low melting point, a tough surface with a rough surface morphology can be formed.
  • the glass frit typically contains Si0 2 in an amount of from about 25 mol.% to about 55 mol.%, in some embodiments from about 30 mol.% to about 50 mol.%, and in some embodiments, from about 35 mol.% to about 45 mol.%.
  • Other oxides may also be employed.
  • alkali metal oxides e.g., Na 2 0 or K 2 0
  • alkali metal oxides may constitute from about 5 mol.% to about 35 mol.%, in some embodiments from about 10 mol.% to about 30 mol.%, and in some embodiments, from about 15 mol.% to about 25 mol.% of the frit.
  • AI 2 0 3 may also be employed in an amount from about 1 mol.% to about 15 mol.%, in some embodiments from about 2 mol.% to about 12 mol.%, and in some embodiments, from about 5 mol.% to about 10 mol.% of the frit.
  • the glass frit may also contain a transition metal oxide (e.g., ZnO) as a melting point suppressant, such as in an amount from about 5 mol.% to about 40 mol.%, in some embodiments from about 10 mol.% to about 35 mol.%, and in some embodiments, from about 15 mol.% to about 30 mol.% of the frit.
  • a transition metal oxide e.g., ZnO
  • Such metal oxide may be present in the glass frit in an amount of 5 wt.% or more, such as 10% wt.% or more, such as 15 wt.% or more, such as 20 wt.% or more, such as 25 wt.% or more to 50 wt.% or less, such as 45 wt.% or less, such as 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less.
  • the coating contains at least one metal oxide.
  • metal oxide may be a metal oxide present in the glass frit.
  • the glass frit may also include oxides that help impart the desired color and to provide a colored glass frit.
  • oxides that help impart the desired color and to provide a colored glass frit.
  • titanium dioxide T1O2
  • T1O2 titanium dioxide
  • B12O3 bismuth oxide
  • B12O3 bismuth oxide
  • B12O3 may constitute from about 10 mol.% to about 50 mol.%, in some embodiments from about 25 mol.% to about 45 mol.%, and in some embodiments, from about 30 mol.% to about 40 mol.% of the frit.
  • the glass frit is typically present in the coating in an amount of about 40 wt.% or more, such as about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more to about 99 wt.% or less, such as about 95 wt.% or less, such as about 90 wt.% or less, such as about 85 wt.% or less, such as about 80 wt.% or less, such as about 70 wt.% or less.
  • concentration may be for a coating after curing and/or after tempering.
  • the glass frit may include particles having a narrow particle diameter distribution. As generally shown in Fig. 2, an example according to the present disclosure may generally have a particle diameter between about 0.1 pm and about 50 pm. However, glass frit according to the present disclosure may have a particle diameter outside of the range disclosed in the example of Fig.
  • greater than about 1 pm such as greater than about 5 pm, such as greater than about 10 pm, such as greater than about 15 pm, such as greater than about 20 pm, such as greater than about 25 pm, such as greater than about 30 pm, such as greater than about 35 pm, such as greater than about 40 pm, such as greater than about 45 pm, such as greater than about 50 pm, such as greater than about 55 pm, such as greater than about 60 pm, such as greater than about 70 pm, such as less than about 100 pm, such as less than about 95 pm, such as less than about 90 pm, such as less than about 85 pm, such as less than about 80 pm, such as less than about 75 pm, such as less than about 70 pm, such as less than about 65 pm.
  • the glass frit may have a D50 of 2 pm or more, such as 2.5 pm or more, such as 3 pm or more, such as 3.5 pm or more, such as 4 pm or more to 7 pm or less, such as 6.5 pm or less, such as 6 pm or less, such as 5.5 pm or less, such as 5 pm or less, such as 4.5 pm or less, such as 4 pm or less.
  • the glass frit may have a D10 of 0.25 pm or more, such as 0.5 pm or more, such as 0.75 pm or more, such as 1 pm or more to 2.5 pm or less, such as 2 pm or less, such as 1.5 pm or less, such as 1.25 pm or less.
  • the glass frit may have a D90 of 6 pm or more, such as 6.5 pm or more, such as 7 pm or more, such as 7.5 pm or more, such as 8 pm or more, such as 8.5 pm or more, such as 9 pm or more, such as 9.5 pm or more, such as 10 pm or more, such as 10.5 pm or more, such as 11 pm or more to 20 pm or less, such as 15 pm or less, such as 14 pm or less, such as 13 pm or less, such as 12.5 pm or less, such as 12 pm or less, such as 11.5 pm or less.
  • the glass frit employed may have a glass transition temperature of 300°C or more, such as 350°C or more, such as 400°C or more, such as 425°C or more, such as 450°C or more, such as 475°C or more, such as 500°C or more, such as 525 °C or more, such as 550 °C or more.
  • the glass transition temperature may be 800°C or less, such as 750°C or less, such as 700°C or less, such as 650°C or less, such as 600°C or less, such as 575°C or less.
  • the coating may also include any number of additives as generally known in the art.
  • these additives may be added to the coating formulation containing the polymerizable compounds.
  • the additives may be present during polymerization and/or crosslinking of the polymerizable compounds and resin.
  • the additives may form covalent bonds with the polymerizable compounds and/or a resin.
  • the coating may include at least one colorant.
  • the colorant may include a pigment, a dye, or a combination thereof.
  • the colorant may be an inorganic pigment (e.g., metallic pigments, white pigments, black pigments, green pigments, red/orange/yellow pigments, etc.), a fluorescent colorant, or a combination thereof.
  • the colorant may be employed to provide a certain color the glass substrate and/or coating.
  • the coating may include at least one light stabilizer.
  • the light stabilizer may comprise a UV absorber (e.g., benzophenones, benzotriazoles, triazines, and combinations thereof), a hindered amine, or a combination thereof.
  • UV absorbers may be employed in the coating to absorb ultraviolet light energy.
  • hindered amine light stabilizers may be employed in the coating to inhibit degradation of the resins and coating thereby providing color stability and extending its durability.
  • a combination of a UV absorber and a hindered amine light stabilizer may be employed.
  • the coating may contain at least one hindered amine light stabilizer (“HALS”).
  • HALS hindered amine light stabilizer
  • Suitable HALS compounds may be piperidine- based compounds. Regardless of the compound from which it is derived, the hindered amine may be an oligomeric or polymeric compound.
  • the compound may have a number average molecular weight of about 1 ,000 or more, in some embodiments from about 1 ,000 to about 20,000, in some embodiments from about 1 ,500 to about 15,000, and in some embodiments, from about 2,000 to about 5,000.
  • low molecular weight hindered amines may also be employed.
  • Such hindered amines are generally monomeric in nature and have a molecular weight of about 1 ,000 or less, in some embodiments from about 155 to about 800, and in some embodiments, from about 300 to about 800.
  • the light stabilizer may be a polymerizable light stabilizer.
  • the polymerizable light stabilizer can be directly attached to a resin, such as a resin in the binder. Such attachment can provide a benefit of minimizing or removing the mobility of the light stabilizer.
  • Such light stabilizers can simply be reacted via a functional group with a functional group of a resin during curing.
  • These polymerizable light stabilizers may contain a carbon-carbon double bond, a hydroxyl group, a carboxyl group, an active ester group, and/or an amine group that allows for the light stabilizer to be covalently attached with the resins.
  • the coating formulation may contain a surfactant.
  • the surfactant may be an anionic surfactant, a cationic surfactant, and/or a non-ionic surfactant.
  • the surfactant may be a non-ionic surfactant.
  • the non-ionic surfactant may be an ethoxylated surfactant, a propoxylated surfactant, an ethoxylated/propoxylated surfactant, polyethylene oxide, an oleate (e.g., sorbitan monooleate, etc.), fatty acid ester or derivative thereof, an alkyl glucoside, a sorbitan alkanoate or a derivative thereof, a combination thereof, etc.
  • an oleate e.g., sorbitan monooleate, etc.
  • fatty acid ester or derivative thereof e.g., an alkyl glucoside, a sorbitan alkanoate or a derivative thereof, a combination thereof, etc.
  • surfactants typically constitute from about 0.001 wt.% to about 2 wt.%, in some embodiments from about 0.005 wt.% to about 1 wt.%, in some embodiments, from about 0.01 wt.% to about 0.5 wt.% of the formulation, and in some embodiments from about 0.1 wt.% to about 0.25 wt.%.
  • the coating formulation may also contain one or more organic solvents.
  • Any solvent capable of dispersing or dissolving the components may be suitable, such as alcohols (e.g., ethanol or methanol); dimethylformamide, dimethyl sulfoxide, hydrocarbons (e.g., pentane, butane, heptane, hexane, toluene and xylene), ethers (e.g., diethyl ether and tetrahydrofuran), ketones and aldehydes (e.g., acetone and methyl ethyl ketone), acids (e.g., acetic acid and formic acid), and halogenated solvents (e.g., dichloromethane and carbon tetrachloride), and so forth.
  • alcohols e.g., ethanol or methanol
  • dimethylformamide dimethyl sulfoxide
  • hydrocarbons e.g., pentane, butane,
  • the coating formulation may also contain water. Although the actual concentration of solvents employed will generally depend on the components of the formulation and the substrate on which it is applied, they are nonetheless typically present in an amount from about 1 wt.% to about 40 wt.%, in some embodiments from about 5 wt.% to about 35 wt.%, and in some embodiments, from about 10 wt.% to about 30 wt.% of the formulation (prior to drying).
  • the coating formulation may contain an initiator and/or a catalyst, such as an acid catalyst.
  • acid catalysts may include, for instance, acetic acid, sulfonic acid, nitric acid, hydrochloric acid, malonic acid, glutaric acid, phosphoric acid, etc., as well as combinations thereof.
  • the initiator may be a
  • photoinitiator that allows for the polymerization of a polymerizable compound, such as an acrylate.
  • a coating formulation 10 comprising a glass frit 12 is applied to a surface of the glass substrate 14.
  • the coating formulation also contains the binder which includes polymerizable compounds 16 (e.g., monomers, oligomers and/or pre-polymers).
  • the coating formulation may also contain metal oxides 18.
  • the coating formulation can be heated to form the coating layer 20 and then cured to form the coating layer 22.
  • techniques may be employed to polymerize the polymerizable compounds. Such techniques may include exposure to UV radiation.
  • the combination of UV radiation and heating can allow for the formation of an interpenetrating network.
  • the heating may allow for hydrolysis and condensation of the polymer network containing the silicon alkoxides (e.g., tetraethyl orthosilicate) and any other alkoxides.
  • Suitable application techniques for applying the coating formulation to the glass substrate may involve, for example, dip coating, drop coating, bar coating, slot-die coating, curtain coating, roll coating, spray coating, printing, etc.
  • the kinematic viscosity of the formulation may be adjusted based on the particular application employed. Typically, however, the kinematic viscosity of the formulation is about 450 centistokes or less, in some embodiments from about 50 to about 400 centistokes, and in some embodiments, from about 100 to about 300 centistokes, as determined with a Zahn cup (#3), wherein the kinematic viscosity is equal to 11.7(t-7.5), where t is the efflux time (in seconds) measured during the test.
  • viscosity modifiers e.g., xylene
  • the coating formulation may be polymerized to form the interpenetrating network.
  • the method of polymerization can be any as generally known in the art.
  • polymerization may be via UV radiation, heating or a combination thereof.
  • only heating may be employed.
  • both UV radiation and heating may be employed to polymerize the various compounds.
  • UV radiation may be employed to polymerize any acrylate compounds.
  • heating may be employed to form the crosslinked polyol and polysiloxane.
  • Such heating and UV exposure may be simultaneous.
  • the heating may be conducted first and the UV light may follow.
  • the UV exposure may be first and the heating may follow.
  • the coating formulation may be heated to polymerize and cure the polymerizable compounds.
  • the coating formulation may be cured at a temperature of from about 50°C to about 350°C, in some embodiments from about 75°C to about 325°C, in some embodiments from about 100°C to about 300°C, in some embodiments from about 150°C to about 300°C, and in some embodiments, from about 200°C to about 300°C for a period of time ranging from about 30 seconds to about 100 minutes, in some embodiments from about 30 seconds to about 50 minutes, in some embodiments from about 1 to about 40 minutes, and in some embodiments, from about 2 to about 15 minutes. Curing may occur in one or multiple steps.
  • the coating formulation may also be optionally dried prior to curing to remove the solvent from the formulation.
  • a pre-drying step may, for instance, occur at a temperature of from about 20°C to about 150°C, in some embodiments from about 30°C to about 125°C, and in some embodiments, from about 40°C to about 100°C.
  • a UV light may be employed to polymerize the compounds.
  • the UV exposure may conducted at an intensity and time period that allows for sufficient polymerization depending on the types of monomers. For instance, for certain acrylates, UV exposure at an intensity of about 15 mW/cm 2 or more, such as about 20 mW/cm 2 or more, such as about 25 mW/cm 2 or more, such as about 30 mW/cm 2 or more for a period of time ranging from about 30 seconds to about 100 minutes, in some embodiments from about 30 seconds to about 50 minutes, in some embodiments from about 1 to about 25 minutes, and in some embodiments, from about 1 to about 10 minutes should be sufficient. In one embodiment, the UV exposure may be from 25 to 30 mW/cm 2 for a period of 5 minutes.
  • UV exposure may be conducted in an inert atmosphere.
  • the exposure may be conducted in the presence of argon gas or nitrogen gas.
  • the UV exposure is conducted in the presence of nitrogen gas.
  • the glass article may also be subjected to an additional heat treatment (e.g., tempering, heat bending, etc.) to further improve the properties of the article.
  • the heat treatment may, for instance, occur at a temperature of from about 500°C to about 800°C, and in some embodiments, from about 550°C to about 750°C.
  • the glass article may also undergo a high-pressure cooling procedure called "quenching.”
  • the cured and/or tempered coating may have a thickness of about 1 micron or more, such as about 5 microns or more, such as about 10 microns or more, such as about 15 microns or more to about 250 microns or less, such as about 150 microns or less, such as about 100 microns or less, such as about 75 microns or less, such as about 60 microns or less, such as about 50 microns or less.
  • the present inventors have discovered that they can provide thinner coatings with the present binder and comparable or even better properties in comparison to coatings containing only one or two binders. However, it should be understood that the thickness of the coating is not necessarily limited by the present invention.
  • the glass may be rendered translucent due to the coating.
  • a coated glass substrate according to the present disclosure may have a percent transparency of less than about 90%, such as less than about 85%, such as less than about 80%, such as less than about 75%, such as less than about 70%, such as less than about 65%, such as less than about 60% and greater than about 30%, such as greater than about 40%, such as greater than about 50%.
  • a coated glass substrate according to the present disclosure may have a percent haze of at least about 50%, such as at least about 60%, such as at least about 70%, such as at least about 75%, such as at least about 80%, such as at least about 85%, such as at least about 90%, such as at least about 95%, such as at least about 99%, such as at least about 100%.
  • a coated glass substrate according to the present disclosure may have a percent clarity of less than about 30%, such as less than about 25%, such as less than about 20%, such as less than about 17.5%, such as less than about 15%, such as less than about 12.5%, such as less than about 10%, such as less than about 7.5%, such as less than about 5%, such as less than about 2.5%.
  • the coated glass substrate may be a translucent coated substrate.
  • such coated glass substrate may have a minimal change in the aforementioned transparency and/or haze parameters. For instance, such change may be within 10%, such as within 7%, such as within 5%, such as within 4%, such as within 3%, such as within 2%, such as within 1%. Such parameters may be within the aforementioned percentages even after a condenser chamber test.
  • the gloss of the coated glass substrate may be variable depending on the degree of measurement.
  • the gloss may be 0.1 or more, such as 0.2 or more, such as 0.5 or more, such as 1 or more, such as 2 or more, such as 5 or more, such as 10 or more to 30 or less, such as 20 or less, such as 15 or less, such as 10 or less, such as 7 or less, such as 5 or less, such as 4 or less, such as 3 or less.
  • the gloss may be 1 or more, such as 2 or more, such as 3 or more, such as 5 or more, such as 8 or more, such as 10 or more, such as 15 or more to 40 or less, such as 30 or less, such as 25 or less, such as 20 or less, such as 15 or less, such as 12 or less, such as 7 or less.
  • the gloss may be determined using any gloss meter as generally known in the art.
  • such coated glass substrate may have a minimal change in the aforementioned gloss parameters. For instance, such change may be within 10%, such as within 7%, such as within 5%, such as within 4%, such as within 3%, such as within 2%, such as within 1%, such as within 0.5%, such as within 0.1%.
  • Such parameters may be within the
  • the coated glass substrate may also be a transparent coated glass substrate.
  • the coated substrate according to the present disclosure may have a percent transparency of greater than about 80%, such as about 85% or more, such as about 90% or more, such as about 93% or more, such as about 95% or more, such as about 97% or more, such as about 98% or more.
  • a coated glass substrate according to the present disclosure may have a percent haze of about 50% or less, such as about 40% or less, such as about 30% or less, such as about 20% or less, such as about 10% or less, such as about 5% or less.
  • a coated glass substrate according to the present disclosure may have a percent clarity of greater than about 20%, such as greater than about 40%, such as greater than about 50%, such as greater than about 75%, such as greater than about 90%.
  • Such values may be within 10%, such as within 8%, such as within 5%, such as within 3%, such as within 2%, such as within 1% of the uncoated, raw glass.
  • the gloss of the coated glass substrate may be variable depending on the degree of measurement.
  • the gloss may be 0.1 or more, such as 1 or more, such as 10 or more, such as 25 or more, such as 50 or more, such as 75 or more, such as 100 or more, such as 125 or more, such as 140 or more to 200 or less, such as 180 or less, such as 160 or less, such as 150 or less.
  • the gloss at 60° may fall within the same ranges.
  • the gloss may be determined using any gloss meter as generally known in the art.
  • the coated glass substrate may have a certain refractive index, in particular at 550 nm.
  • the refractive index may be 1.2 or more, such as 1.25 or more, such as 1.3 or more to 1.7 or less, such as 1.6 or less, such as 1.5 or less, such as 1.45 or less, such as 1.4 or less, such as 1.38 or less, such as 1.35 or less.
  • Coating Thickness The coated layer of as coated glass is removed by a razor. The step height of the coating is observed using a profilometer. The data is an average measured from three points at different positions.
  • Atomic Force Microscopy The topography is investigated by an atomic force microscope (AFM, AP-0100, Parker Sci. Instrument). The non- contact method, preferred for soft surface in general is used. The size of the sample is about 2 cm by 2 cm and the scanning area is 5,000 microns by 5,000 microns. The scanning speed of 20 microns/second. The surface roughness is quantitatively characterized by measuring the arithmetic average roughness and root mean square roughness.
  • Cross-Hatch Adhesion The cross-hatch adhesion is determined in accordance with ASTM D3359-09. For the test, cuts a certain distance apart are made in the coating depending on the thickness of the coating. Additionally, intersecting cuts are also made. Tape is placed on the grid area and within approximately 90 seconds of application, the tape is removed by pulling it off rapidly at as close to an angle of 180° as possible. The grid area is inspected for removal of coating from the substrate. The classifications go from 0B to 5B wherein 5B indicates that none of the squares of the lattice are detached. A value of less than 3B is indicative of a failure.
  • XPS Measurements XPS data was acquired with a PHI Quantum 2000 unit using a probe beam of focused, monochromatic Al Ka radiation (1486.6 eV). The analysis area was 600 microns and the take-off angle and the acceptance angle were about 45° and +/- 23°, respectively. The sputter rate was -100 Angstroms/minute (S1O2 equivalent) and ion gun condition was Ar+ (2 keV, 2 mm by 2 mm raster). The atomic composition and chemistry of the sample surface is determined. The escape depth of the photoelectrons limits the depth of the analysis to the outer -50 Angstroms. The typical detection limits for most other elements is 0.1 to 1 atomic %. The data presented includes general survey scans, which give the full spectrum between 0 and 1100 eV binding energy.
  • SEM Scanning Electron Microscopy
  • Stud Pull Strength The adhesive strength of the coating can be evaluated by measuring the stud pull strength. The coating surface is blown with nitrogen gas. An aluminum dolly with a diameter of 20 mm is polished by sand paper (100#). An aldehyde-amine condensate/organocopper compound mixture (Loctite 736) is sprayed on the surface of the coating and an aluminum stud. After 5 minutes, an acrylic adhesive (312) s added to the surface of the aluminum stud and it is glued to the surface of the coating with pressure until solid adhesion is achieved. The glued aluminum stud and glass are placed at room temperature for 3 hours. The dolly is pulled by a PosiTest AT with a pull rate of 30 psi/sec. The adhesive strength is measured by the PosiTest AT. A strength of less than 450 psi is considered a failure.
  • Transparency was measured by Hunter UltraScan XE with model of TTRIN from 350 nm to 1050 nm. Tvis% is calculated according to the following equation.
  • Tuv% of antimicrobial glass at UV range is measured by UV-vis (Peking Elmer 950) and Tuv% is calculated by following equation.
  • Water Boil Test The water boil test follows the testing procedure of TP319 (Guardian Ind.). Glass is immersed in one beaker filled with De-ion water at 100°C. After 10 min, the glass is removed from boiling water and dried by N 2 gas before measurement. The change of T% will be calculated by the difference of T% before and after water boil test. The specification of water boil test is DT% ⁇ ⁇ 0.5%.
  • NaOH Solution (0.1 N) Test NaOH test follows the testing procedure of TP301-7B (Guardian Ind.). Glass is immersed by NaOH solution (0.1 N) filled in one beaker at room temperature. After 1 hour, the glass is taken from solution, rinsed by De-ion water and dried by N 2 gas. The change of T% will be calculated by the difference of T% before and after NaOH testing. The specification of water boil test is DT% ⁇ ⁇ 0.5%.
  • Tape Pull Test follows the testing procedure of TP- 201 -7 (Guardian Ind.). The tape (3179C, 3M) is placed on the surface of the glass by applying pressure. After 1.5 minutes, the tape is pulled out quickly with hand and the residual adhesive of tape will be removed with tissue paper (AccuWipe) soaked by NPA. The change of T% will be calculated by the difference of T% before and after tape pull test. The specification of tape pull test is DT% ⁇ 1.5%.
  • Crockmeter Test Crockmeter test follows the testing procedure of TP-209 (Guardian Ind.; Crockmeter: SDL Atlas CM-5). The size of glass is 3” x 3” and total test cycle number is 750. The weight of arm is 345 g. The change of T% will be calculated by the difference of T% before and after crockmeter test. The specification of crockmeter test is DT% ⁇ 1.5%.
  • Brush Test G with size of 2”x3” is mounted on chamber filled with Dl water and brush with size of 2”x4” is used to scratch the surface of as coated glass.
  • the cycle number of brush including back and forth motion is 1000.
  • the surface of“as coated” glass is exanimated by microscopy after testing and no clear scratch on film will be the sign of passing test.
  • the change of T% will be calculated by the difference of T% before and after brush test.
  • Taber Abrasion Test Glass with size as 4”x4” is amounted on sample holder of Taber (Model 5130 Abraser). Abrasion wheel is CS-10F and cycle number is 5. The change of T% will be calculated by the difference of T% before and after abrasion test.
  • High Humidity and High Temperature Chamber Test Glass is set inside chamber with 85°C and 85% of humidity for 10 days. The change of T% will be calculated by the difference of T% before and after testing.
  • Ammonium Solution Test 10% of NH 4 OH solution is prepared by diluting of 29% of NH4OH solution with Dl water. Antimicrobial glass is soaked inside solution and T% is measured before and after soaking of 5 days. The change of T% will be calculated by the difference of T% before and after testing.
  • Windex Test Glass is soaked inside 100% of Windex solution and T% is measured before and after soaking of 5 days. The change of T% will be calculated by the difference of T% before and after testing.
  • Condense Chamber Test Water Fog: Glass is set in chamber with 45°C and 100% of humidity for 21 days. T% before and after testing is measured. Meanwhile, adhesive strength of coated layer after testing is investigated by cross- hatch and no more 15% of film can be removed in order to pass test. The change of T% will be calculated by the difference of T% before and after testing.
  • Copper Accelerated Acetic Acid Salt Spray (CASS) Test Glass is set in CASS chamber for 120 hours (5 days). The solution used in CASS test is made by 0.94 g of CuCh, 4.6 g of acetic acid and 258 g of NaCI. The chamber temperature is 49°C and pressure is 18 psi, respectively. The pH of solution is in the range from 3.1 to 3.3. The specification of CASS chamber test is DT% ⁇ 1.5%. The change of T% will be calculated by the difference of T% before and after testing.
  • Freeze Thaw Chamber Test Glass with size as 3”x3” is set freeze thaw chamber for 10 days. Humidity is in the range from 50-85% and temperature range is from -40°C to 85°C. The change of T% will be calculated by the difference of T% before and after testing.
  • the glass frits utilized in the samples had the following compositions:
  • the polystyrene-co-methyl methacrylate copolymer binder included the following:
  • the monomer formulation (429-98-1) included the following:
  • the entire binder including the PSMMA binder and monomer formulation 429-98-1 contains three parts including a polyisocyanate-polyol resin, an epoxy acrylate, and polystyrene-co-methyl methacrylate.
  • a polyisocyanate-polyol resin an epoxy acrylate
  • polystyrene-co-methyl methacrylate To a 200 ml_ glass jar, 10 grams of blocked polyisocyanate, 40 grams of epoxy oligomer, 8 grams of crosslinking agent, and 5 grams of polyol were added. Then 20 ml_ of xylene and butanol were added separately. The solution was mixed by a stir bar for 1 hour at room temperature and mixed with 15% of polystyrene-co-methyl methacrylate in mixed solvent of xylene and butanol with the ratio of 5 to 30.
  • the initiator solution (421-37-1) included the following:
  • the AgO nanoparticle solution included the following:
  • the coating formulation was prepared by adding the glass frit to a 100 mL jar and then the PSMMA binder/429-98-1. Then the initiator solution and any surfactant were added to the jar. The solution was diluted by a mixed solvent of xylene and butanol. The solution was then ground by ball mill and five cubic aluminum type grading media. The ball mill time was at least 3 days.
  • a coating formulation containing a glass frit with zinc oxide and titanium dioxide and polymerizable compounds for the formation of an IPN was applied to one surface of a glass substrate.
  • the coating formulation employed in the samples is summarized in the table below.
  • the coating formulation was applied to a glass substrate and cured at a low temperature.
  • the glass substrate with the coating was then tempered to form a coated glass substrate.
  • the XPS analysis indicates the presence of titanium around 1.59 wt.% and zinc around 15.19 wt.%, after conversion from atomic %, on the surface of coating of the glass.
  • FIG. 3 shows that a coating according to the present disclosure may exhibit about a 54% reduction in the amount of methylene blue when the solution has been irradiated for about 10 minutes.
  • a coating formulation containing a glass frit with zinc oxide, silver oxide, and polymerizable compounds for the formation of an IPN was applied to one surface of a glass substrate.
  • the coating formulation employed in the samples is summarized in the table below.
  • the coating formulation was applied to a glass substrate and cured at a low temperature.
  • the glass substrate with the coating was then tempered to form a coated glass substrate.
  • the XPS analysis indicates the presence of titanium dioxide and zinc oxide around the surface of the coating of the glass.
  • the comparative sample was the same as sample 456-79-5 except without the presence of the AgO solution.
  • the coating formulation was applied to a glass substrate and cured at a low temperature. The samples were tested to assess their optical and mechanical properties.
  • sample 450-144-2 translucent glass
  • Staphylococcus aureus ATCC 6538
  • Escherichia coli ATCC 8739
  • the sample and the control were coated by a solution containing the microorganisms and the number of microorganisms was counted before and after testing.
  • the table below, as well as FIG. 4, summarizes the results. In can be seen from the table that the percent reduction for both S. aureus and E. coli is higher than 99.9%, indicating excellent antimicrobial performance.
  • Coating sol formulations were prepared according to the following tables.
  • the coating formulation was prepared according to the following table. The solution was cloudy when adding the zinc oxide nanoparticles.
  • the adhesive strength of the coating can be evaluated by tape pull.
  • the data indicates that there is excellent bonding between the coating layer and the glass substrate.
  • the decrease in T% may be accredited to a rougher surface after rubbing with tissue paper soaked with NPA.
  • Antimicrobial performance of the sample is evaluated by procedure JIS Z2801 using two microorganisms, Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 8739) under testing conditions of 36°C for 24 hours.
  • the sample and the control were coated by a solution containing the microorganisms and the number of microorganisms was counted before and after testing.
  • the table below summarizes the results. In can be seen from the table that the percent reduction for both S. aureus and E. coli is higher than 99.9%, indicating excellent antimicrobial performance.
  • the XPS analysis indicates the presence of zinc around 38.68 wt.%, after conversion from atomic %, on the surface of coating of the glass.
  • Coating sol formulations were prepared according to the following tables. The formulation for Sol 6 was mixed for 24 hours before using while the formulation for Sol 7 was mixed at room temperature for 3 days until the cloudy sol was changed to transparent.
  • the coating formulation was prepared according to the following table.
  • the solution was mixed at room temperature for 24 hours before using.
  • Soda lime glass plates with a 4 mm thickness and size of 3” by 3” were rubbed by solution of cesium oxide (2%) and washed with liquid soap. The plates were rinsed by deionized water and dried by nitrogen gas. The film was coated on the glass plate by spin coating with the sol formulation above. The spin coating speed was 1300 rpm and the ramp was 255 rps. Using a pipette, 1.5 ml_ of sol was transferred to the air side of the glass mounted in a sample stage of a spin coater. The spin coating time was 30 seconds. The back side of the coated glass was cleaned with tissue paper soaked with IPA after spin coating. The coated glass was heated in a box furnace at 680 degrees Celsius for 6 minutes.
  • Antimicrobial performance of the sample is evaluated by procedure JIS Z2801 using two microorganisms, Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 8739) under testing conditions of 36°C for 24 hours.
  • the sample and the control were coated by a solution containing the microorganisms and the number of microorganisms was counted before and after testing.
  • the table below summarizes the results. In can be seen from the table that the percent reduction for both S. aureus and E. coli is higher than 99.9%, indicating excellent antimicrobial performance.
  • a coating formulation is prepared according to the following.
  • the polymer binder comprises three parts: the first binder comes from polyisocyanate- polyol resin, the second binder comes from the epoxy acrylate, and the last one comes from the polystyrene-co-methyl methacrylate.
  • the binder formulation can be prepared by adding the polyisocyanate, epoxy oligomer, crosslinking agent, and polyol to a glass jar. Then, xylene and butanol can be added separately. The solution is mixed by stir bar for 1 hour at room temperature and then mixed with 15% polystyrene-methyl methacrylate in the mixed solvent of xylene and butanol at a weight ratio of 5 to 30.
  • the coating solution is prepared by combining the polymer binder with the glass frit.
  • the glass frit and zinc oxide are added to a jar and then the polymer binder is added.
  • the PEG 1900 surfactant is added with the initiator solution, which is prepared by dissolved 0.25 g of benzoyl peroxide into 10 mL of xylene.
  • the solution is diluted using a mixture of xylene and butanol.
  • the solution is ground using a ball mill (US Stoneware) and five cubic aluminum type grading media (US Stoneware Brun 050-90). The ball mill time was at least 3 days.
  • the coating formulations are as follows:
  • “As coated” glass is prepared using a glass with size as 8”x12” and a thickness of 4 mm. The glass is washed by 1% of Ce0 2 solution and rinsed by tap water. Then, the glass is washed by soap and thoroughly rinsed by De-ion water. Finally, glass is dried by N 2 gas. The glass is coated using a coating machine (BYK) and a bird bar with sizes as 3 mil is set in front of glass. The coating speed is set as 50 mm/sec. The coated glass is immediately moved to the oven to be cured at 250°C for 20 min to create“as coated” glass. “As coated” glass should demonstrate certain green strength and may be further fabricated without damage on surface. Finally,“as coated” glass is heated at the oven with 680°C for 14 min to develop tempered glass. Tempered glass should show excellent adhesive and mechanical strength. During tempered process, glass frits will be melted and adhered on glass plate strongly.
  • Antimicrobial performance is evaluated by procedure JIS Z2801 using two microorganisms, Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 8739) under testing conditions of 36°C for 24 hours.
  • the sample and the control were coated by a solution containing the microorganisms and the number of microorganisms was counted before and after testing.
  • the table below summarizes the results. In can be seen from the table that the percent reduction for both S. aureus and E. coli is higher than 99.9%, indicating excellent antimicrobial performance.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Composite Materials (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Plant Pathology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Surface Treatment Of Glass (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un substrat de verre à couche. Le substrat de verre à couche comprend un revêtement contenant au moins un oxyde métallique contenant un oxyde de zinc. Le zinc de l'oxyde de zinc est présent en une proportion de 5 % en poids à 50 % en poids telle que déterminée selon une spectroscopie XPS. Le substrat de verre à couche présente une rugosité de surface Sa ou Sq d'environ 5 nm à environ 1 500 nm telle que déterminée par l'intermédiaire d'une microscopie à force atomique.
PCT/IB2019/054734 2018-06-08 2019-06-06 Verre antimicrobien pouvant être traité thermiquement WO2019239265A1 (fr)

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KR1020207032668A KR20210019410A (ko) 2018-06-08 2019-06-06 열처리성 항미생물 유리
JP2020563642A JP2021526116A (ja) 2018-06-08 2019-06-06 熱処理可能な抗菌ガラス
US16/973,151 US20210246069A1 (en) 2018-06-08 2019-06-06 Heat-treatable antimicrobial glass
BR112020024941-6A BR112020024941A2 (pt) 2018-06-08 2019-06-06 Vidro antimicrobiano tratável por calor
CA3098016A CA3098016A1 (fr) 2018-06-08 2019-06-06 Verre antimicrobien pouvant etre traite thermiquement
EP19742911.1A EP3802444A1 (fr) 2018-06-08 2019-06-06 Verre antimicrobien pouvant être traité thermiquement

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021140346A1 (fr) * 2020-01-10 2021-07-15 Nanophos Sa Suspensions auto-liantes comprenant des nanoparticules de dioxyde de titane et d'oxyde de zinc et substrats revêtus préparés au moyen de ces suspensions auto-liantes
WO2022098618A1 (fr) * 2020-11-06 2022-05-12 Corning Incorporated Substrats présentant des performances électrostatiques améliorées
EP4095109A3 (fr) * 2021-03-19 2023-01-25 Viavi Solutions Inc. Article doté d'une surface optique avec des fonctions modifiées

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000072487A (ja) * 1998-08-27 2000-03-07 Nippon Electric Glass Co Ltd 抗菌性結晶化ガラス物品及びその製造方法
US20160075883A1 (en) * 2013-04-25 2016-03-17 The Ohio State University Methods of fabricating superhydrophobic, optically transparent surfaces
WO2017095987A1 (fr) * 2015-12-02 2017-06-08 Guardian Industries Corporation Article en verre présentant un revêtement ayant un réseau polymère interpénétrant
WO2018223110A1 (fr) * 2017-06-02 2018-12-06 Guardian Glass, LLC Article en verre contenant un revêtement ayant un réseau polymère interpénétrant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000072487A (ja) * 1998-08-27 2000-03-07 Nippon Electric Glass Co Ltd 抗菌性結晶化ガラス物品及びその製造方法
US20160075883A1 (en) * 2013-04-25 2016-03-17 The Ohio State University Methods of fabricating superhydrophobic, optically transparent surfaces
WO2017095987A1 (fr) * 2015-12-02 2017-06-08 Guardian Industries Corporation Article en verre présentant un revêtement ayant un réseau polymère interpénétrant
WO2018223110A1 (fr) * 2017-06-02 2018-12-06 Guardian Glass, LLC Article en verre contenant un revêtement ayant un réseau polymère interpénétrant

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021140346A1 (fr) * 2020-01-10 2021-07-15 Nanophos Sa Suspensions auto-liantes comprenant des nanoparticules de dioxyde de titane et d'oxyde de zinc et substrats revêtus préparés au moyen de ces suspensions auto-liantes
WO2022098618A1 (fr) * 2020-11-06 2022-05-12 Corning Incorporated Substrats présentant des performances électrostatiques améliorées
EP4095109A3 (fr) * 2021-03-19 2023-01-25 Viavi Solutions Inc. Article doté d'une surface optique avec des fonctions modifiées

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JP2021526116A (ja) 2021-09-30
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KR20210019410A (ko) 2021-02-22
US20210246069A1 (en) 2021-08-12
WO2019239265A9 (fr) 2020-04-23

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